U.S. patent number 8,778,221 [Application Number 13/594,916] was granted by the patent office on 2014-07-15 for aromatic amide compound.
This patent grant is currently assigned to Ticona LLC. The grantee listed for this patent is Steven D. Gray, Kamlesh P. Nair. Invention is credited to Steven D. Gray, Kamlesh P. Nair.
United States Patent |
8,778,221 |
Nair , et al. |
July 15, 2014 |
Aromatic amide compound
Abstract
An aromatic amide compound having the following general formula
(I) is provided: ##STR00001## wherein, X.sub.1 and X.sub.2 are
independently C(O)HN or NHC(O); G.sub.1, G.sub.2 and G.sub.3 are
independently hydrogen, C(O)HN-phenyl, or NHC(O)-phenyl, wherein at
least one of G.sub.1, G.sub.2 and G.sub.3 is C(O)HN-phenyl or
NHC(O)-phenyl; Q.sub.1, Q.sub.2, and Q.sub.3 are independently
hydrogen, C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of
Q.sub.1, Q.sub.2, and Q.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl;
R.sub.5 is halo, haloalkyl, alkyl, alkenyl, aryl, heteroaryl,
cycloalkyl, or heterocyclyl; and m is from 0 to 4.
Inventors: |
Nair; Kamlesh P. (Florence,
KY), Gray; Steven D. (Mequon, WI) |
Applicant: |
Name |
City |
State |
Country |
Type |
Nair; Kamlesh P.
Gray; Steven D. |
Florence
Mequon |
KY
WI |
US
US |
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Assignee: |
Ticona LLC (Florence,
KY)
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Family
ID: |
46759121 |
Appl.
No.: |
13/594,916 |
Filed: |
August 27, 2012 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20130048911 A1 |
Feb 28, 2013 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61528445 |
Aug 29, 2011 |
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61664911 |
Jun 27, 2012 |
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Current U.S.
Class: |
252/299.01;
564/156; 564/143; 564/155; 564/153; 252/299.5 |
Current CPC
Class: |
C07C
233/80 (20130101); C09K 19/22 (20130101); C07C
231/02 (20130101); C09K 19/54 (20130101); C09K
19/38 (20130101); C08L 77/12 (20130101); C08K
5/20 (20130101); C09K 2019/0481 (20130101) |
Current International
Class: |
C09K
19/38 (20060101); C09K 19/54 (20060101); C07C
233/65 (20060101); C07C 233/80 (20060101); C07C
231/02 (20060101) |
Field of
Search: |
;564/123,142,152,153,155,156 ;252/299.01,299.5 |
References Cited
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EP |
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EP |
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0 852 249 |
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1 095 930 |
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EP |
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WO |
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WO |
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Jul 2004 |
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WO |
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WO 2007/038373 |
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Apr 2007 |
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WO |
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|
Primary Examiner: Wu; Shean C
Attorney, Agent or Firm: Dority & Manning, P.A.
Parent Case Text
RELATED APPLICATIONS
The present application claims priority to U.S. provisional
applications Ser. No. 61/528,445, filed on Aug. 29, 2011, and
61/664,911, filed on Jun. 27, 2012, which are incorporated herein
in their entirety by reference thereto.
Claims
What is claimed is:
1. An aromatic amide compound having the following general formula
(II): ##STR00019## wherein, G.sub.1, G.sub.2 and G.sub.3 are
independently hydrogen, C(O)HN-phenyl, or NHC(O)-phenyl, wherein at
least one of G.sub.1, G.sub.2 and G.sub.3 is C(O)HN-phenyl or
NHC(O)-phenyl; and Q.sub.1, Q.sub.2, and Q.sub.3 are independently
hydrogen, C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of
Q.sub.1, Q.sub.2, and Q.sub.3 is C(O)HN-phenyl or
NHC(O)-phenyl.
2. The compound of claim 1, wherein G.sub.3 and Q.sub.3 are
hydrogen.
3. The compound of claim 2, wherein G.sub.1 and Q.sub.1 are
hydrogen and G.sub.2 and Q.sub.2 selected from C(O)NH-phenyl or
NHC(O)-phenyl.
4. The compound of claim 2, wherein G.sub.2 and Q.sub.2 are
hydrogen and G.sub.1 and Q.sub.1 are selected from C(O)NH-phenyl or
NHC(O)-phenyl.
5. An aromatic amide compound having, wherein the compound is
provided by general (III): ##STR00020## wherein, G.sub.1, G.sub.2
and G.sub.3 are independently hydrogen, C(O)HN-phenyl, or
NHC(O)-phenyl, wherein at least one of G.sub.1, G.sub.2 and G.sub.3
is C(O)HN-phenyl or NHC(O)-phenyl; Q.sub.1, Q.sub.2, and Q.sub.3
are independently hydrogen, C(O)HN-phenyl, or NHC(O)-phenyl,
wherein at least one of Q.sub.1, Q.sub.2, and Q.sub.3 is
C(O)HN-phenyl or NHC(O)-phenyl; and Y.sub.1, Y.sub.2, and Y.sub.3
are independently hydrogen, C(O)HN-phenyl, or NHC(O)-phenyl, and
wherein at least one of Y.sub.1, Y.sub.2, and Y.sub.3 is
C(O)HN-phenyl or NHC(O)-phenyl.
6. The compound of claim 5, wherein Y.sub.3, G.sub.3 and Q.sub.3
are hydrogen.
7. The compound of claim 6, wherein Y.sub.1, G.sub.1, and Q.sub.1
are hydrogen and Y.sub.2, G.sub.2 and Q.sub.2 are selected from
C(O)NH-phenyl or NHC(O)-phenyl.
8. The compound of claim 6, wherein Y.sub.2, G.sub.2 and Q.sub.2
are hydrogen and Y.sub.1, G.sub.1 and Q.sub.1 are selected from
C(O)NH-phenyl or NHC(O)-phenyl.
9. The compound of claim 1, wherein the compound is
N1,N3-bis(4-benzamidophenyl)benzene-1,3-dicarboxamide or
N1,N3-bis(3-benzamidophenyl)benzene-1,3-dicarboxamide.
10. The compound of claim 5, wherein the compound is
N1,N3,N5-tris(4-benzamidophenyl)benzene-1,3,5-tricarboxamide.
11. A polymer composition comprising the compound of claim 1 and a
polymer.
12. The polymer composition of claim 11, wherein the polymer is a
thermotropic liquid crystalline polymer.
13. The polymer composition of claim 12, wherein the polymer is a
wholly aromatic liquid crystalline polymer.
14. A method for forming an aromatic amide compound, the method
comprising: reacting an aromatic acyl chloride with an
amine-substituted phenyl to form an aminophenyl amide precursor;
and thereafter, reacting the precursor with an isophthaloyl
chloride, trimesoyl chloride, or a combination thereof to form a
compound having the following general formula (I): ##STR00021##
wherein, X.sub.1 and X.sub.2 are independently C(O)HN or NHC(O);
G.sub.1, G.sub.2 and G.sub.3 are independently hydrogen,
C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of G.sub.1,
G.sub.2 and G.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl; Q.sub.1,
Q.sub.2, and Q.sub.3 are independently hydrogen, C(O)HN-phenyl, or
NHC(O)-phenyl, wherein at least one of Q.sub.1, Q.sub.2, and
Q.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl; R.sub.5 is halo,
haloalkyl, alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, or
heterocyclyl; and m is from 0 to 4.
15. The method of claim 14, wherein the aromatic acyl chloride is
benzoyl chloride.
16. The method of claim 14, wherein the amine-substituted phenyl is
1,3-phenyldiamine or 1,4-phenyldiamine.
17. The method of claim 14, wherein the precursor is an aminophenyl
substituted benzamide.
18. The method of claim 14, wherein the precursor is reacted with
isophthaloyl chloride.
19. The method of claim 14, wherein the precursor is reacted with
trimesoyl chloride.
20. A polymer composition comprising the compound of claim 5 and a
polymer.
21. The polymer composition of claim 20, wherein the polymer is a
thermotropic liquid crystalline polymer.
22. The polymer composition of claim 20, wherein the polymer is a
wholly aromatic liquid crystalline polymer.
Description
BACKGROUND OF THE INVENTION
High performance polymers, such as thermotropic liquid crystalline
polymers ("LCPs"), are often used to form molded parts (e.g.,
electrical connectors). One benefit of such polymers is that they
can exhibit a relatively high "flow", which refers to the ability
of the polymer when heated under shear to uniformly fill complex
parts at fast rates without excessive flashing or other detrimental
processing issues. In addition to enabling complex part geometries,
high polymer flow can also enhance the ultimate performance of the
molded part. Most notably, parts generated from well-flowing
polymers generally display improved dimensional stability owing to
the lower molded-in stress, which makes the component more amenable
to downstream thermal processes that can be negatively impacted
from warpage and other polymer stress relaxation processes that
occur in less well-molded materials. Despite their relatively high
flow capacity, many high performance polymers still fall short of
what is needed to meet the increased molding demands of intricate
part designs without significant compromises to the final product
performance. As such, a need continues to exist for a new compound
that can be used in combination with high performance polymers,
among other possible uses.
SUMMARY OF THE INVENTION
In accordance with one embodiment of the present invention, an
aromatic amide compound is disclosed that has the following general
formula (I):
##STR00002## wherein,
X.sub.1 and X.sub.2 are independently C(O)HN or NHC(O);
G.sub.1, G.sub.2 and G.sub.3 are independently hydrogen,
C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of G.sub.1,
G.sub.2 and G.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl;
Q.sub.1, Q.sub.2, and Q.sub.3 are independently hydrogen,
C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of Q.sub.1,
Q.sub.2, and Q.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl;
R.sub.5 is halo, haloalkyl, alkyl, alkenyl, aryl, heteroaryl,
cycloalkyl, or heterocyclyl; and
m is from 0 to 4.
In accordance with another embodiment of the present invention, a
method for forming an aromatic amide compound, such as represented
above in formula (I), is disclosed. The method comprises reacting
an aromatic acyl chloride with an amine-substituted phenyl to form
an aminophenyi amide precursor, and thereafter, reacting the
precursor with an aromatic diacyl chloride, aromatic triacyl
chloride, or a combination thereof.
Other features and aspects of the present invention are set forth
in greater detail below.
BRIEF DESCRIPTION OF THE FIGURES
A full and enabling disclosure of the present invention, including
the best mode thereof to one skilled in the art, is set forth more
particularly in the remainder of the specification, including
reference to the accompanying figures, in which:
FIG. 1 is the Proton NMR characterization for
N1,N3-bis(4-benzamidophenyl)benzene-1,3-dicarboxamide (Compound
A2); and
FIG. 2 is the Proton NMR characterization for
N1,N3-bis(3-benzamidophenyl)benzene-1,3-dicarboxamide (Compound
B2); and
FIG. 3 is the Proton NMR characterization for
N1,N3,N5-tris(4-benzamidophenyl)benzene-1,3,5-tricarboxamide
(Compound C).
DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS
Definitions
It is to be understood that the terminology used herein is for the
purpose of describing particular embodiments only and is not
intended to limit the scope of the present invention.
"Alkyl" refers to monovalent saturated aliphatic hydrocarbyl groups
having from 1 to 10 carbon atoms and, in some embodiments, from 1
to 6 carbon atoms. "C.sub.x-yalkyl" refers to alkyl groups having
from x to y carbon atoms. This term includes, by way of example,
linear and branched hydrocarbyl groups such as methyl (CH.sub.3),
ethyl (CH.sub.3CH.sub.2), n-propyl (CH.sub.3CH.sub.2CH.sub.2),
isopropyl ((CH.sub.3).sub.2CH), n-butyl
(CH.sub.3CH.sub.2CH.sub.2CH.sub.2), isobutyl
((CH.sub.3).sub.2CHCH.sub.2), sec-butyl
((CH.sub.3)(CH.sub.3CH.sub.2)CH), t-butyl ((CH.sub.3).sub.3C),
n-pentyl (CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2), and neopentyl
((CH.sub.3).sub.3CCH.sub.2).
"Alkenyl" refers to a linear or branched hydrocarbyl group having
from 2 to 10 carbon atoms and in some embodiments from 2 to 6
carbon atoms or 2 to 4 carbon atoms and having at least 1 site of
vinyl unsaturation (>C.dbd.C<). For example,
(C.sub.x-C.sub.y)alkenyl refers to alkenyl groups having from x to
y carbon atoms and is meant to include for example, ethenyl,
propenyl, 1,3-butadienyl, and so forth.
"Alkynyl" refers to refers to a linear or branched monovalent
hydrocarbon radical containing at least one triple bond. The term
"alkynyl" may also include those hydrocarbyl groups having other
types of bonds, such as a double bond and a triple bond.
"Aryl" refers to an aromatic group of from 3 to 14 carbon atoms and
no ring heteroatoms and having a single ring (e.g., phenyl) or
multiple condensed (fused) rings (e.g., naphthyl or anthryl). For
multiple ring systems, including fused, bridged, and Spiro ring
systems having aromatic and non-aromatic rings that have no ring
heteroatoms, the term "Aryl" applies when the point of attachment
is at an aromatic carbon atom (e.g., 5,6,7,8
tetrahydronaphthalene-2-yl is an aryl group as its point of
attachment is at the 2-position of the aromatic phenyl ring).
"Cycloalkyl" refers to a saturated or partially saturated cyclic
group of from 3 to 14 carbon atoms and no ring heteroatoms and
having a single ring or multiple rings including fused, bridged,
and spiro ring systems. For multiple ring systems having aromatic
and non-aromatic rings that have no ring heteroatoms, the term
"cycloalkyl" applies when the point of attachment is at a
non-aromatic carbon atom (e.g.
5,6,7,8,-tetrahydronaphthalene-5-yl). The term "cycloalkyl"
includes cycloalkenyl groups, such as adamantyl, cyclopropyl,
cyclobutyl, cyclopentyl, cyclooctyl, and cyclohexenyl. The term
"cycloalkenyl" is sometimes employed to refer to a partially
saturated cycloalkyl ring having at least one site of
>C.dbd.C< ring unsaturation.
"Halo" or "halogen" refers to fluoro, chloro, bromo, and iodo.
"Haloalkyl" refers to substitution of alkyl groups with 1 to 5 or
in some embodiments 1 to 3 halo groups.
"Heteroaryl" refers to an aromatic group of from 1 to 14 carbon
atoms and 1 to 6 heteroatoms selected from oxygen, nitrogen, and
sulfur and includes single ring (e.g. imidazolyl) and multiple ring
systems (e.g. benzimidazol-2-yl and benzimidazol-6-yl). For
multiple ring systems, including fused, bridged, and spiro ring
systems having aromatic and non-aromatic rings, the term
"heteroaryl" applies if there is at least one ring heteroatom and
the point of attachment is at an atom of an aromatic ring (e.g.
1,2,3,4-tetrahydroquinolin-6-yl and
5,6,7,8-tetrahydroquinolin-3-yl). In some embodiments, the nitrogen
and/or the sulfur ring atom(s) of the heteroaryl group are
optionally oxidized to provide for the N oxide (N.fwdarw.O),
sulfinyl, or sulfonyl moieties. Examples of heteroaryl groups
include, but are not limited to, pyridyl, furanyl, thienyl,
thiazolyl, isothiazolyl, triazolyl, imidazolyl, imidazolinyl,
isoxazolyl, pyrrolyl, pyrazolyl, pyridazinyl, pyrimidinyl, purinyl,
phthalazyl, naphthylpryidyl, benzofuranyl, tetrahydrobenzofuranyl,
isobenzofuranyl, benzothiazolyl, benzoisothiazolyl, benzotriazolyl,
indolyl, isoindolyl, indolizinyl, dihydroindolyl, indazolyl,
indolinyl, benzoxazolyl, quinolyl, isoquinolyl, quinolizyl,
quianazolyl, quinoxalyl, tetrahydroquinolinyl, isoquinolyl,
quinazolinonyl, benzimidazolyl, benzisoxazolyl, benzothienyl,
benzopyridazinyl, pteridinyl, carbazolyl, carbolinyl,
phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl,
phenoxazinyl, phenothiazinyl, and phthalimidyl.
"Heterocyclic" or "heterocycle" or "heterocycloalkyl" or
"heterocyclyl" refers to a saturated or partially saturated cyclic
group having from 1 to 14 carbon atoms and from 1 to 6 heteroatoms
selected from nitrogen, sulfur, or oxygen and includes single ring
and multiple ring systems including fused, bridged, and spiro ring
systems. For multiple ring systems having aromatic and/or
non-aromatic rings, the terms "heterocyclic", "heterocycle",
"heterocycloalkyl", or "heterocyclyl" apply when there is at least
one ring heteroatom and the point of attachment is at an atom of a
non-aromatic ring (e.g. decahydroquinolin-6-yl). In some
embodiments, the nitrogen and/or sulfur atom(s) of the heterocyclic
group are optionally oxidized to provide for the N oxide, sulfinyl,
sulfonyl moieties. Examples of heterocyclyl groups include, but are
not limited to, azetidinyl, tetrahydropyranyl, piperidinyl,
N-methylpiperidin-3-yl, piperazinyl, N-methylpyrrolidin-3-yl,
3-pyrrolidinyl, 2-pyrrolidon-1-yl, morpholinyl, thiomorpholinyl,
imidazolidinyl, and pyrrolidinyl.
It should be understood that the aforementioned definitions
encompass unsubstituted groups, as well as groups substituted with
one or more other functional groups as is known in the art. For
example, an aryl, heteroaryl, cycloalkyl, or heterocyclyl group may
be substituted with from 1 to 8, in some embodiments from 1 to 5,
in some embodiments from 1 to 3, and in some embodiments, from 1 to
2 substituents selected from alkyl, alkenyl, alkynyl, alkoxy, acyl,
acylamino, acyloxy, amino, quaternary amino, amide, imino, amidino,
aminocarbonylamino, amidinocarbonylamino, aminothiocarbonyl,
aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy,
aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, aryl, aryloxy,
arylthio, azido, carboxyl, carboxyl ester, (carboxyl ester)amino,
(carboxyl ester)oxy, cyano, cycloalkyl, cycloalkyloxy,
cycloalkylthio, guanidino, halo, haloalkyl, haloalkoxy, hydroxy,
hydroxyamino, alkoxyamino, hydrazino, heteroaryl, heteroaryloxy,
heteroarylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio,
nitro, oxo, thione, phosphate, phosphonate, phosphinate,
phosphonamidate, phosphorodiamidate, phosphoramidate monoester,
cyclic phosphoramidate, cyclic phosphorodiamidate, phosphoramidate
diester, sulfate, sulfonate, sulfonyl, substituted sulfonyl,
sulfonyloxy, thioacyl, thiocyanate, thiol, alkylthio, etc., as well
as combinations of such substituents.
"Compound" as used herein refers to a compound encompassed by the
generic formulae disclosed herein, any subgenus of those generic
formulae, and any forms of the compounds within the generic and
subgeneric formulae, including the racemates, stereoisomers,
tautomers, and salts of the compound.
"Stereoisomer" or "stereoisomers" refer to compounds that differ in
the chirality of one or more stereocenters. Stereoisomers include
enantiomers and diastereomers.
"Racemates" refers to a mixture of enantiomers.
"Tautomer" refer to alternate forms of a compound that differ in
the position of a proton, such as enol keto and imine enamine
tautomers, or the tautomeric forms of heteroaryl groups containing
a ring atom attached to both a ring NH moiety and a ring .dbd.N
moiety such as pyrazoles, imidazoles, benzimidazoles, triazoles,
and tetrazoles.
"Liquid crystalline polymer" or "liquid crystal polymer" refers to
a polymer that can possess a rod-like structure that allows it to
exhibit liquid crystalline behavior in its molten state (e.g.,
thermotropic nematic state). The polymer may contain aromatic units
(e.g., aromatic polyesters, aromatic polyesteramides, etc.) so that
it is wholly aromatic (e.g., containing only aromatic units) or
partially aromatic (e.g., containing aromatic units and other
units, such as cycloaliphatic units). The polymer may also be fully
crystalline or semi-crystalline in nature.
DETAILED DESCRIPTION
It is to be understood by one of ordinary skill in the art that the
present discussion is a description of exemplary embodiments only,
and is not intended as limiting the broader aspects of the present
invention.
The present invention is generally directed to an aromatic amide
compound having the following general formula (I):
##STR00003## wherein,
X.sub.1 and X.sub.2 are independently C(O)HN or NHC(O);
G.sub.1, G.sub.2 and G.sub.3 are independently hydrogen,
C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of G.sub.1,
G.sub.2 and G.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl;
Q.sub.1, Q.sub.2, and Q.sub.3 are independently hydrogen,
C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of Q.sub.1,
Q.sub.2, and Q.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl;
R.sub.5 is halo, haloalkyl, alkyl, alkenyl, aryl, heteroaryl,
cycloalkyl, or heterocyclyl; and
m is from 0 to 4.
In certain embodiments, the compound is a di-functional compound in
that the core phenyl ring is directly bonded to only two (2) amide
groups (e.g., C(O)HN or NHC(O)). In such embodiments, m in Formula
(I) may be 0. One particular embodiment of such a compound has the
following general formula (II):
##STR00004##
wherein, G.sub.1, G.sub.2, Q.sub.1, and Q.sub.2 are as defined
above. For instance, G.sub.3 and Q.sub.3 are typically hydrogen.
Further, in some embodiments, G.sub.1 and Q.sub.1 may be hydrogen
and G.sub.2 and Q.sub.2 may be C(O)NH-phenyl or NHC(O)-phenyl.
Alternatively, G.sub.2 and Q.sub.2 may be hydrogen and G.sub.1 and
Q.sub.1 may be C(O)NH-phenyl or NHC(O)-phenyl.
Of course, the core phenyl ring may also be directly bonded to
three (3) or more amide groups. For example, one particular
embodiment of such a compound is provided by general (III):
##STR00005## wherein,
G.sub.1, G.sub.2, G.sub.3, Q.sub.1, Q.sub.2, and Q.sub.3 are as
defined above; and
Y.sub.1, Y.sub.2, and Y.sub.3 are independently hydrogen,
C(O)HN-phenyl, or NHC(O)-phenyl, wherein at least one of Y.sub.1,
Y.sub.2, and Y.sub.3 is C(O)HN-phenyl or NHC(O)-phenyl. For
example, Y.sub.3, G.sub.3 and Q.sub.3 are typically hydrogen.
Further, in some embodiments, Y.sub.1, G.sub.1, and Q.sub.1 may be
hydrogen and Y.sub.2, G.sub.2 and Q.sub.2 may be C(O)NH-phenyl or
NHC(O)-phenyl. Alternatively, Y.sub.2, G.sub.2 and Q.sub.2 may be
hydrogen and Y.sub.1, G.sub.1 and Q.sub.1 may be C(O)NH-phenyl or
NHC(O)-phenyl.
Specific embodiments of the aromatic amide compound of the present
invention are also set forth in the table below:
TABLE-US-00001 Cmpd MW # Structure Name (g/mol) A1 ##STR00006##
N4-phenyl-N1-[3-[[4- (phenylcarbamoyl)- benzoyl]amino]
phenyl]terephthalamide 554.6 A2 ##STR00007## N1,N3-bis(4-
benzamidophenyl)benzene- 1,3-dicarboxamide 554.6 B1 ##STR00008##
N3-phenyl-N1-[3-[[3- (phenylcarbamoyl)benzoyl]- amino]phenyl]
benzene-1,3-dicarboxamide 554.6 B2 ##STR00009## N1,N3-bis(3-
benzamidophenyl)benzene- 1,3-dicarboxamide 554.6 C ##STR00010##
N1,N3,N5-tris(4- benzamidophenyl)benzene- 1,3,5-tricarboxamide
792.8 D ##STR00011## N1,N3,N5-tris(3- benzamidophenyl)benzene-
1,3,5-tricarboxamide 792.8
The compounds disclosed herein may be prepared using a variety of
different techniques. For example, a precursor aminophenyl amide
may initially be formed by a nucleophilic addition/elimination
reaction between an aromatic acyl chloride (e.g., benzoyl chloride)
and a phenyl substituted with one or more amines (e.g., amine,
diamine, triamine, etc.). Particular examples of such
amine-substituted phenyls include 1,3-phenyldiamine and
1,4-phenyldiamine. The location of amine substitution on the phenyl
ring can influence the resulting stereochemistry of the amide
precursor. For example, the reaction of a benzoyl chloride with
1,3-phenyldiamine may result in a 3-aminophenyl substituted
benzamide precursor having the following structure:
##STR00012##
Likewise, a reaction with 1,4-phenyldiamine may result in a
4-aminophenyl substituted benzamide precursor having the following
structure:
##STR00013##
Regardless, the resulting amide precursor may be further reacted
with a diacyl and/or triacyl chloride to achieve the desired
compound. Diacyl chlorides (e.g., isophthaloyl chloride), for
instance, typically result in "ditopic" compounds in which the core
phenyl ring is bonded to only two amide groups, while triacyl
chlorides (e.g., trimesoyl chloride) typically result in "tritopic"
compounds in which the core phenyl ring is bonded to three amide
groups. Such techniques for forming the compound of the present
invention are described in more detail in the examples below. It
will be appreciated that where process conditions (i.e., reaction
temperatures, times, mole ratios of reactants, solvents, pressures,
etc.) are given, other process conditions can also be used unless
otherwise stated. Optimum reaction conditions may vary with the
particular reactants or solvent used, but such conditions can be
determined by one skilled in the art by routine optimization
procedures. Additionally, as will be apparent to those skilled in
the art, compounds that contain one or more chiral centers can be
prepared or isolated as pure stereoisomers, i.e., as individual
enantiomers or diastereomers, or as stereoisomer-enriched mixtures.
All such stereoisomers (and enriched mixtures) are included within
the scope of this invention. Pure stereoisomers (or enriched
mixtures) may be prepared using, for example, optically active
starting materials or stereoselective reagents well-known in the
art. Alternatively, racemic mixtures of such compounds can be
separated using, for example, chiral column chromatography, chiral
resolving agents and so forth.
The compound of the present invention may have a variety of
different uses. For instance, the present inventors have discovered
that they can act as flow aids for thermotropic liquid crystalline
polymers by altering intermolecular polymer chain interactions,
thereby lowering the overall viscosity of the polymer matrix under
shear. In addition to simply reducing viscosity, the aromatic amide
compound may not be easily volatized or decomposed during
compounding, molding, and/or use. This minimizes off-gassing and
the formation of blisters that would otherwise impact the final
mechanical properties of a part made from the polymer composition.
Without intending to be limited by theory, it is believed that
active hydrogen atoms of the amide functional groups are capable of
forming a hydrogen bond with the backbone of liquid crystalline
polyesters or polyesteramides. Such hydrogen bonding strengthens
the attachment of the compound to the liquid crystalline polymer
matrix and thus minimizes the likelihood that it becomes
volatilized during formation. While providing the benefits noted,
the aromatic amide compound does not generally react with the
polymer backbone of the liquid crystalline polymer to any
appreciable extent so that the mechanical properties of the polymer
are not adversely impacted.
When employed as a flow aid, the aromatic amide compound of the
present invention typically has a relatively low molecular weight.
For example, the compound may have a molecular weight of about
2,500 grams per mole or less, in some embodiments from about 200 to
about 1,500 grams per mole, in some embodiments from about 300 to
about 1,200 grams per mole, and in some embodiments, from about 400
to about 1,000 grams per mole. The compound may also generally
possess a high amide functionality so it is capable of undergoing a
sufficient degree of hydrogen bonding with the liquid crystalline
polymer. The degree of amide functionality for a given molecule may
be characterized by its "amide equivalent weight", which reflects
the amount of a compound that contains one molecule of an amide
functional group and may be calculated by dividing the molecular
weight of the compound by the number of amide groups in the
molecule. For example, the aromatic amide compound may contain from
4 to 8, and in some embodiments, from 4 to 6 amide functional
groups per molecule. The amide equivalent weight may likewise be
from about 10 to about 1,000 grams per mole or less, in some
embodiments from about 50 to about 500 grams per mole, and in some
embodiments, from about 100 to about 300 grams per mole.
The type of thermotropic liquid crystalline polymers that may be
employed in combination with the compound of the present invention
can vary as is known in the art. Suitable liquid crystalline
polymers are generally condensation polymers that have relatively
rigid and linear polymer chains so that they melt to form a liquid
crystalline phase. Examples of such polymers may include, for
instance, aromatic or aliphatic polyesters, aromatic or aliphatic
poly(esteramides), aromatic or aliphatic poly(estercarbonates),
aromatic or aliphatic polyamides, etc. Such polymers may, for
example, contain repeating units formed from one or more aromatic
or aliphatic hydroxycarboxylic acids, aromatic or aliphatic
dicarboxylic acids, aromatic or aliphatic diols, aromatic or
aliphatic aminocarboxylic acids, aromatic or aliphatic amines,
aromatic or aliphatic diamines, etc., as well as combinations
thereof.
Particularly suitable aromatic polyesters are obtained by
polymerizing (1) two or more aromatic hydroxycarboxylic acids; (2)
at least one aromatic hydroxycarboxylic acid, at least one aromatic
dicarboxylic acid, and at least one aromatic diol; and/or (3) at
least one aromatic dicarboxylic acid and at least one aromatic
diol. Examples of suitable aromatic hydroxycarboxylic acids
include, 4-hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic
acid; 2-hydroxy-6-naphthoic acid; 2-hydroxy-5-naphthoic acid;
3-hydroxy-2-naphthoic acid; 2-hydroxy-3-naphthoic acid;
4'-hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl-4-benzoic acid;
4'-hydroxyphenyl-3-benzoic acid, etc., as well as alkyl, alkoxy,
aryl and halogen substituents thereof. Examples of suitable
aromatic dicarboxylic acids include terephthalic acid; isophthalic
acid; 2,6-naphthalenedicarboxylic acid; diphenyl
ether-4,4'-dicarboxylic acid; 1,6-naphthalenedicarboxylic acid;
2,7-naphthalenedicarboxylic acid; 4,4'-dicarboxybiphenyl;
bis(4-carboxyphenyl)ether; bis(4-carboxyphenyl)butane;
bis(4-carboxyphenyl)ethane; bis(3-carboxyphenyl)ether;
bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl
and halogen substituents thereof. Examples of suitable aromatic
diols include hydroquinone; resorcinol; 2,6-dihydroxynaphthalene;
2,7-dihydroxynaphthalene; 1,6-dihydroxynaphthalene;
4,4'-dihydroxybiphenyl; 3,3'-dihydroxybiphenyl;
3,4'-dihydroxybiphenyl; 4,4'-dihydroxybiphenyl ether;
bis(4-hydroxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl
and halogen substituents thereof. In one particular embodiment, the
aromatic polyester contains monomer repeat units derived from
4-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid. The monomer
units derived from 4-hydroxybenzoic acid may constitute from about
45% to about 85% (e.g., 73%) of the polymer on a mole basis and the
monomer units derived from 2,6-hydroxynaphthoic acid may constitute
from about 15% to about 55% (e.g., 27%) of the polymer on a mole
basis. Such aromatic polyesters are commercially available from
Ticona, LLC under the trade designation VECTRA.RTM. A. The
synthesis and structure of these and other aromatic polyesters may
be described in more detail in U.S. Pat. Nos. 4,161,470; 4,473,682;
4,522,974; 4,375,530; 4,318,841; 4,256,624; 4,219,461; 4,083,829;
4,184,996; 4,279,803; 4,337,190; 4,355,134; 4,429,105; 4,393,191;
4,421,908; 4,434,262; and 5,541,240.
Liquid crystalline polyesteramides may also include those obtained
by polymerizing (1) at least one aromatic hydroxycarboxylic acid
and at least one aromatic aminocarboxylic acid; (2) at least one
aromatic hydroxycarboxylic acid, at least one aromatic dicarboxylic
acid, and at least one aromatic amine and/or diamine optionally
having phenolic hydroxy groups; and (3) at least one aromatic
dicarboxylic acid and at least one aromatic amine and/or diamine
optionally having phenolic hydroxy groups. Suitable aromatic amines
and diamines may include, for instance, 3-aminophenol;
4-aminophenol; 1,4-phenylenediamine; 1,3-phenylenediamine, etc., as
well as alkyl, alkoxy, aryl and halogen substituents thereof. In
one particular embodiment, the aromatic polyesteramide contains
monomer units derived from 2,6-hydroxynaphthoic acid, terephthalic
acid, and 4-aminophenol. The monomer units derived from
2,6-hydroxynaphthoic acid may constitute from about 35% to about
85% of the polymer on a mole basis (e.g., 60%), the monomer units
derived from terephthalic acid may constitute from about 5% to
about 50% (e.g., 20%) of the polymer on a mole basis, and the
monomer units derived from 4-aminophenol may constitute from about
5% to about 50% (e.g., 20%) of the polymer on a mole basis. Such
aromatic polyesters are commercially available from Ticona, LLC
under the trade designation VECTRA.RTM. B. In another embodiment,
the aromatic polyesteramide contains monomer units derived from
2,6-hydroxynaphthoic acid, and 4-hydroxybenzoic acid, and
4-aminophenol, as well as other optional monomers (e.g.,
4,4'-dihydroxybiphenyl and/or terephthalic acid). The synthesis and
structure of these and other aromatic poly(esteramides) may be
described in more detail in U.S. Pat. Nos. 4,339,375; 4,355,132;
4,351,917; 4,330,457; 4,351,918; and 5,204,443.
The liquid crystalline polymer typically has a number average
molecular weight (Mn) of about 2,000 grams per mole or more, in
some embodiments from about 4,000 grams per mole or more, and in
some embodiments, from about 5,000 to about 30,000 grams per mole.
Of course, it is also possible to form polymers having a lower
molecular weight, such as less than about 2,000 grams per mole. The
intrinsic viscosity of the polymer composition, which is generally
proportional to molecular weight, may likewise be about 2
deciliters per gram ("dL/g") or more, in some embodiments about 3
dL/g or more, in some embodiments from about 4 to about 20 dL/g,
and in some embodiments from about 5 to about 15 dL/g. Intrinsic
viscosity may be determined in accordance with ISO-1628-5 using a
50/50 (v/v) mixture of pentafluorophenol and hexafluoroisopropanol,
as described in more detail below.
The relative proportion of the liquid crystalline polymer and the
aromatic amide compound may be selected to help achieve a balance
between viscosity and mechanical properties. More particularly,
high aromatic amide compound contents can result in low viscosity,
but too high of a content may reduce the viscosity to such an
extent that the compound adversely impacts the melt strength of the
polymer blend. In most embodiments, for example, the aromatic amide
compound, or mixtures thereof, may be employed in an amount of from
about 0.1 to about 5 parts, in some embodiments from about 0.2 to
about 4 parts, and in some embodiments, from about 0.3 to about 1.5
parts by weight relative to 100 parts by weight of the liquid
crystalline polymer. Aromatic amide compounds may, for example,
constitute from about 0.1 wt. % to about 5 wt. %, in some
embodiments from about 0.2 wt. % to about 4 wt. %, and in some
embodiments, from about 0.3 wt. % to about 1.5 wt. % of the polymer
composition. Liquid crystalline polymers may likewise constitute
from about 95 wt. % to about 99.9 wt. %, in some embodiments from
about 96 wt. % to about 98.8 wt. %, and in some embodiments, from
about 98.5 wt. % to about 99.7 wt. % of the polymer
composition.
The manner in which the compound and the liquid crystalline polymer
are combined may vary as is known in the art. For instance, the raw
materials may be supplied either simultaneously or in sequence to a
melt processing device that dispersively blends the materials.
Batch and/or continuous melt processing techniques may be employed.
For example, a mixer/kneader, Banbury mixer, Farrel continuous
mixer, single-screw extruder, twin-screw extruder, roll mill, etc.,
may be utilized to blend and melt process the materials. One
particularly suitable melt processing device is a co-rotating,
twin-screw extruder (e.g., Leistritz co-rotating fully intermeshing
twin screw extruder). Such extruders may include feeding and
venting ports and provide high intensity distributive and
dispersive mixing. For example, the liquid crystalline polymer and
compound may be fed to the same or different feeding ports of a
twin-screw extruder and melt blended to form a substantially
homogeneous melted mixture. Melt blending may occur under high
shear/pressure and heat to ensure sufficient dispersion. For
example, melt processing may occur at a temperature of from about
50.degree. C. to about 500.degree. C., and in some embodiments,
from about 100.degree. C. to about 250.degree. C. Likewise, the
apparent shear rate during melt processing may range from about 100
seconds-1 to about 10,000 seconds-1, and in some embodiments, from
about 500 seconds-1 to about 1,500 seconds-1. Of course, other
variables, such as the residence time during melt processing, which
is inversely proportional to throughput rate, may also be
controlled to achieve the desired degree of homogeneity.
Besides melt blending, other techniques may also be employed to
combine the compound and the liquid crystalline polymer. For
example, the compound may be supplied during one or more stages of
the polymerization of the liquid crystalline polymer. In such
embodiments, it is typically desired to apply the compound before
melt polymerization has been initiated, and typically in
conjunction with the precursor monomers for the liquid crystalline
polymer. Regardless of the manner in which it is introduced, the
aromatic amide compound may lower the melt viscosity of the
resulting polymer composition, The melt viscosity may, for
instance, be reduced so that the ratio of the starting liquid
crystalline polymer viscosity to the blended composition viscosity
is at least about 1.1, in some embodiments at least about 1.2, in
some embodiments from about 1.5 to about 50, in some embodiments
from about 2 to about 40, and in some embodiments, from about 4 to
about 30. In one particular embodiment, the polymer composition may
have a melt viscosity of from about 0.5 to about 100 Pa-s, in some
embodiments from about 1 to about 80 Pa-s, and in some embodiments,
from about 2 to about 50 Pa-s, determined at a shear rate of 1000
seconds-1. Melt viscosity may be determined in accordance with ISO
Test No. 11443 (equivalent to ASTM Test No. 1238-70) at a
temperature of 350.degree. C. The melting point of the polymer
composition may also range from about 250.degree. C. to about
400.degree. C., in some embodiments from about 270.degree. C. to
about 380.degree. C., and in some embodiments, from about
300.degree. C. to about 360.degree. C. Likewise, the
crystallization temperature may range from about 200.degree. C. to
about 400.degree. C., in some embodiments from about 250.degree. C.
to about 350.degree. C., and in some embodiments, from about
280.degree. C. to about 320.degree. C. The melting and
crystallization temperatures may be determined as is well known in
the art using differential scanning calorimetry ("DSC"), such as
determined by ISO Test No. 11357.
If desired, the resulting polymer composition may also be combined
with a wide variety of other types of components to form a filled
composition. For example, a filler material may be incorporated
with the polymer composition to enhance strength. A filled
composition can include a filler material such as a fibrous filler
and/or a mineral filler and optionally one or more additional
additives as are generally known in the art.
Mineral fillers may, for instance, be employed in the polymer
composition to help achieve the desired mechanical properties
and/or appearance. When employed, mineral fillers typically
constitute from about 5 wt. % to about 60 wt. %, in some
embodiments from about 10 wt. % to about 55 wt. %, and in some
embodiments, from about 20 wt. % to about 50 wt. % of the polymer
composition. Clay minerals may be particularly suitable for use in
the present invention. Examples of such clay minerals include, for
instance, talc (Mg.sub.3Si.sub.4O.sub.10(OH).sub.2), halloysite
(Al.sub.2Si.sub.2O.sub.5(OH).sub.4), kaolinite
(Al.sub.2Si.sub.2O.sub.5(OH).sub.4), illite
((K,H.sub.3O)(Al,Mg,Fe).sub.2(Si,Al).sub.4O.sub.10[(OH).sub.2,(H.sub.2O)]-
), montmorillonite
(Na,Ca).sub.0.33(Al,Mg).sub.2Si.sub.4O.sub.10(OH).sub.2.nH.sub.2O),
vermiculite
((MgFe,Al).sub.3(Al,Si).sub.4O.sub.10(OH).sub.2.4H.sub.2O),
palygorskite ((Mg,Al).sub.2Si.sub.4O.sub.10(OH).4(H.sub.2O)),
pyrophyllite (Al.sub.2Si.sub.4O.sub.10(OH).sub.2), etc., as well as
combinations thereof. In lieu of, or in addition to, clay minerals,
still other mineral fillers may also be employed. For example,
other suitable silicate fillers may also be employed, such as
calcium silicate, aluminum silicate, mica, diatomaceous earth,
wollastonite, and so forth. Mica, for instance, may be particularly
suitable. There are several chemically distinct mica species with
considerable variance in geologic occurrence, but all have
essentially the same crystal structure. As used herein, the term
"mica" is meant to generically include any of these species, such
as muscovite (KAl.sub.2(AlSi.sub.3)O.sub.10(OH).sub.2), biotite
(K(Mg,Fe).sub.3(AlSi.sub.3)O.sub.10(OH).sub.2), phlogopite
(KMg.sub.3(AlSi.sub.3)O.sub.10(OH).sub.2), lepidolite
(K(Li,Al).sub.2-3(AlSi.sub.3)O.sub.10(OH).sub.2), glauconite
(K,Na)(Al,Mg,Fe).sub.2(Si,Al).sub.4O.sub.10(OH).sub.2), etc., as
well as combinations thereof.
Fibers may also be employed as a filler material to further improve
the mechanical properties. Such fibers generally have a high degree
of tensile strength relative to their mass. For example, the
ultimate tensile strength of the fibers (determined in accordance
with ASTM D2101) is typically from about 1,000 to about 15,000
Megapascals ("MPa"), in some embodiments from about 2,000 MPa to
about 10,000 MPa, and in some embodiments, from about 3,000 MPa to
about 6,000 MPa. To help maintain an insulative property, which is
often desirable for use in electronic components, the high strength
fibers may be formed from materials that are also generally
insulative in nature, such as glass, ceramics (e.g., alumina or
silica), aramids (e.g., Kevlar.RTM. marketed by E. I. duPont de
Nemours, Wilmington, Del.), polyolefins, polyesters, etc., as well
as mixtures thereof. Glass fibers are particularly suitable, such
as E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass,
S2-glass, etc., and mixtures thereof.
The volume average length of the fibers may be from about 50 to
about 400 micrometers, in some embodiments from about 80 to about
250 micrometers, in some embodiments from about 100 to about 200
micrometers, and in some embodiments, from about 110 to about 180
micrometers. The fibers may also have a narrow length distribution.
That is, at least about 70% by volume of the fibers, in some
embodiments at least about 80% by volume of the fibers, and in some
embodiments, at least about 90% by volume of the fibers have a
length within the range of from about 50 to about 400 micrometers,
in some embodiments from about 80 to about 250 micrometers, in some
embodiments from about 100 to about 200 micrometers, and in some
embodiments, from about 110 to about 180 micrometers. The fibers
may also have a relatively high aspect ratio (average length
divided by nominal diameter) to help improve the mechanical
properties of the resulting polymer composition. For example, the
fibers may have an aspect ratio of from about 2 to about 50, in
some embodiments from about 4 to about 40, and in some embodiments,
from about 5 to about 20 are particularly beneficial. The fibers
may, for example, have a nominal diameter of about 10 to about 35
micrometers, and in some embodiments, from about 15 to about 30
micrometers.
The relative amount of the fibers in the filled polymer composition
may also be selectively controlled to help achieve the desired
mechanical properties without adversely impacting other properties
of the composition, such as its flowability. For example, the
fibers may constitute from about 2 wt. % to about 40 wt. %, in some
embodiments from about 5 wt. % to about 35 wt. %, and in some
embodiments, from about 6 wt. % to about 30 wt. % of the polymer
composition. Although the fibers may be employed within the ranges
noted above, small fiber contents may be employed while still
achieving the desired mechanical properties. For example, the
fibers can be employed in small amounts such as from about 2 wt. %
to about 20 wt. %, in some embodiments, from about 5 wt. % to about
16 wt. %, and in some embodiments, from about 6 wt. % to about 12
wt. %.
Still other additives that can be included in the composition may
include, for instance, antimicrobials, pigments (e.g., carbon
black), antioxidants, stabilizers, surfactants, waxes, solid
solvents, and other materials added to enhance properties and
processability. Lubricants, for instance, may be employed in the
polymer composition. Examples of such lubricants include fatty
acids esters, the salts thereof, esters, fatty acid amides, organic
phosphate esters, and hydrocarbon waxes of the type commonly used
as lubricants in the processing of engineering plastic materials,
including mixtures thereof. Suitable fatty acids typically have a
backbone carbon chain of from about 12 to about 60 carbon atoms,
such as myristic acid, palmitic acid, stearic acid, arachic acid,
montanic acid, octadecinic acid, parinric acid, and so forth.
Suitable esters include fatty acid esters, fatty alcohol esters,
wax esters, glycerol esters, glycol esters and complex esters.
Fatty acid amides include fatty primary amides, fatty secondary
amides, methylene and ethylene bisamides and alkanolamides such as,
for example, palmitic acid amide, stearic acid amide, oleic acid
amide, N,N'-ethylenebisstearamide and so forth. Also suitable are
the metal salts of fatty acids such as calcium stearate, zinc
stearate, magnesium stearate, and so forth; hydrocarbon waxes,
including paraffin waxes, polyolefin and oxidized polyolefin waxes,
and microcrystalline waxes. Particularly suitable lubricants are
acids, salts, or amides of stearic acid, such as pentaerythritol
tetrastearate, calcium stearate, or N,N'-ethylenebisstearamide.
When employed, the lubricant(s) typically constitute from about
0.05 wt. % to about 1.5 wt. %, and in some embodiments, from about
0.1 wt. % to about 0.5 wt. % (by weight) of the polymer
composition.
The present invention may be better understood with reference to
the following examples.
Test Methods
Melt Viscosity:
The melt viscosity (Pa-s) was determined in accordance with ISO
Test No. 11443 at 350.degree. C. and at a shear rate of 400
s.sup.-1 and 1000 s.sup.-1 using a Dynisco 7001 capillary
rheometer. The rheometer orifice (die) had a diameter of 1 mm,
length of 20 mm, LID ratio of 20.1, and an entrance angle of
180.degree.. The diameter of the barrel was 9.55 mm.+-.0.005 mm and
the length of the rod was 233.4 mm.
Intrinsic Viscosity:
The intrinsic viscosity ("IV") may be measured in accordance with
ISO-1628-5 using a 50/50 (v/v) mixture of pentafluorophenol and
hexafluoroisopropanol. Each sample was prepared in duplicate by
weighing about 0.02 grams into a 22 mL vial. 10 mL of
pentafluorophenol ("PFP") was added to each vial and the solvent.
The vials were placed in a heating block set to 80.degree. C.
overnight. The following day 10 mL of hexafluoroisopropanol
("HFIP") was added to each vial. The final polymer concentration of
each sample was about 0.1%. The samples were allowed to cool to
room temperature and analyzed using a PolyVisc automatic
viscometer.
Melting and Crystallization Temperatures:
The melting temperature ("Tm") and crystallization temperature
("Tc") were determined by differential scanning calorimetry ("DSC")
as is known in the art. The melting temperature is the differential
scanning calorimetry (DSC) peak melt temperature as determined by
ISO Test No. 11357. The crystallization temperature is determined
from the cooling exotherm in the cooling cycle. Under the DSC
procedure, samples were heated and cooled at 20.degree. C. per
minute as stated in ISO Standard 10350 using DSC measurements
conducted on a TA 02000 Instrument.
Tensile Properties:
Tensile properties are tested according to ISO Test No. 527
(technically equivalent to ASTM D638). Modulus and strength
measurements are made on the same test strip sample having a length
of 80 mm, thickness of 10 mm, and width of 4 mm. The testing
temperature is 23.degree. C., and the testing speeds are 1 or 5
mm/min.
Flexural Properties:
Flexural properties are tested according to ISO Test No. 178
(technically equivalent to ASTM D790). This test is performed on a
64 mm support span. Tests are run on the center portions of uncut
ISO 3167 multi-purpose bars. The testing temperature is 23.degree.
C. and the testing speed is 2 mm/min.
Notched Charpy Impact Strength:
Notched Charpy properties are tested according to ISO Test No. ISO
179-1) (technically equivalent to ASTM D256, Method B). This test
is run using a Type A notch (0.25 mm base radius) and Type 1
specimen size (length of 80 mm, width of 10 mm, and thickness of 4
mm). Specimens are cut from the center of a multi-purpose bar using
a single tooth milling machine. The testing temperature is
23.degree. C.
Synthesis of N1,N3-bis(4-benzamidophenyl)benzene-1,3-dicarboxamide
Compound A2
The synthesis of Compound A2 from 1,4-phenylene diamine,
terephthaloyl chloride, and benzoyl chloride may be performed
according to the following scheme:
##STR00014##
The experimental setup consisted of a 500 mL glass beaker equipped
with a magnetic stirrer. 1,4 phenylene diamine (20 g) was dissolved
in warm N-methyl pyrrolidone ("NMP") (200 mL) at 40.degree. C.
Benzoyl chloride (26.51 g) was added drop wise to a stirred
solution of the diamine over a period of 30 minutes. After the
addition of the benzoyl chloride was completed, the reaction
mixture was warmed to 70-80.degree. C. and then allowed to cool to
50.degree. C. After cooling to the desired temperature,
isophthaloyl chloride (18.39 g) was added in small portions such
that the temperature of the reaction mixture did not increase above
70.degree. C. The mixture was then stirred for additional one (1)
hour at 70.degree. C., and was allowed to rest overnight at room
temperature. The product was recovered by addition of water (200
mL) to the reaction mixture, followed by filtration and washing
with hot water (500 mL). The product was then dried in a vacuum
oven at 150.degree. C. for about 6-8 hours to give a pale yellow
colored solid (yield ca. 90%). The melting point by DSC analysis
was determined to be 329.degree. C. The Proton NMR characterization
for the compound is also shown in FIG. 1.
Synthesis of N1,N3-bis(3-benzamidophenyl)benzene-1,3-dicarboxamide
Compound B2
The synthesis of Compound B2 from 1,3-phenylene diamine,
isophthaloyl chloride, and benzoyl chloride may be performed
according to the following scheme:
##STR00015##
The experimental setup consisted of a 500 mL glass beaker equipped
with a magnetic stirrer. 1,3 phenylene diamine (20 g) was dissolved
in warm dimethylacetamide ("DMAc") (200 mL) at 40.degree. C.
Benzoyl chloride (26.51 g) was added drop wise to a stirred
solution of the diamine over a period of 30 minutes. After the
addition of the benzoyl chloride was completed, the reaction
mixture was warmed to 70-80.degree. C. and allowed to cool to
50.degree. C. After cooling to the desired temperature,
isophthaloyl chloride (18.39 g) was added in small portions such
that the temperature of the reaction mixture did not increase above
70.degree. C. The mixture was then stirred for additional one hour
at 70.degree. C., and was allowed to rest overnight at room
temperature. The product was recovered by addition of water (200
mL) to the reaction mixture, followed by filtration and washing
with hot water (500 mL). The product was then dried in a vacuum
oven at 150.degree. C. for about 6-8 hours to give a pale yellow
colored solid (yield ca. 90%). The melting point by DSC analysis
was determined to be 226.degree. C. The Proton NMR characterization
for the compound is shown in FIG. 2.
Synthesis of
N1,N3,N5-tris(4-benzamidophenyl)benzene-1,3,5-tricarboxamide
Compound C
The synthesis of Compound C from trimesoyl chloride and
4-benzoanilide may be performed according to the following
scheme:
##STR00016##
The experimental set up consisted of a 1 L glass beaker equipped
with a glass rod stirrer coupled with an overhead mechanical
stirrer. Trimesoyl chloride (27.08 g) was dissolved in DMAc (100
mL) at room temperature. 4-aminobenzanilide (69.3 g) was dissolved
in DMAc (100 mL). The amine solution was gradually added to the
acid chloride solution over a period of 15 minutes, and the
reaction mixture was then stirred and the temperature increased to
90.degree. C. for about 3 hours. The mixture was allowed to rest
overnight at room temperature. The product was recovered by
precipitation through the addition of 1.5 L of distilled water,
which was followed by was vacuum filtration using a filter paper
and a Buchner funnel. The crude product was then washed with
acetone (500 mL) and washed again with hot water (1 L). The product
was then air dried over night at room temperature and then was
dried in a vacuum oven 150.degree. C. for 4 to 6 hours. The product
(68 g) was a bright yellow solid.
Compound C can also be synthesized by a different synthetic
route--i.e., from trimesoyl chloride and 1,4-phenylene diamine as
follows:
##STR00017##
The experimental set up consisted of a 2 L glass beaker equipped
with a glass rod stirrer coupled with an overhead mechanical
stirrer. 1,4 phenylene diamine (250.41 g) was dissolved in warm
dimethyl acetamide (1.5 L) (alternatively N-methyl pyrrolidone can
also be used) and maintained at 45.degree. C. Next benzoyl chloride
(332.11 g) was slowly added drop wise over a period of 1.5 to 2
hours, to the amine solution with constant stirring. The rate of
addition of the benzoyl chloride was maintained such that the
reaction temperature was maintained less than 60.degree. C. After
complete addition of the benzoyl chloride, the reaction mixture was
gradually warmed to 85-90.degree. C. and then allowed to cool to
around 45-50.degree. C. At this point, trimesoyl chloride (200.7 g)
was gradually added to the reaction mixture such that the exotherm
did not increase the reaction temperature above 60.degree. C. After
complete addition of the trimesoyl chloride, the reaction mixture
was allowed to stir for additional 45 minutes, after which the
reaction temperature was increased to 90.degree. C. for about 30
minutes and then was cooled to room temperature. The mixture was
allowed to rest overnight at room temperature. The product was
recovered by precipitation through the addition of 1.5 L of
distilled water, which was followed by was vacuum filtration using
a filter paper and a Buchner funnel. The crude product was then
washed with acetone (1 L) and washed again with hot water (2 L).
The product (520 g, yield: ca. 87%) was then air dried over night
at room temperature and then was dried in a vacuum oven 150.degree.
C. for 4 to 6 hours. The product was a pale tan solid.
The Proton NMR characterization for the compound is shown in FIG.
3.
Synthesis of
N1,N3,N5-tris(3-benzamidophenyl)benzene-1,3,5-tricarboxamide
Compound D
The synthesis of Compound D from trimesoyl chloride, benzoyl
chloride and 1,3-phenylene diamine can be performed according to
the following scheme:
##STR00018##
The experimental set up consisted of a 1 L glass beaker equipped
with a glass rod stirrer coupled with an overhead mechanical
stirrer. 1,3 phenylene diamine (20 g) was dissolved in warm
dimethyl acetamide (200 mL) (alternatively N-methyl pyrrolidone can
also be used) and maintained at 45.degree. C. Next benzoyl chloride
(26.51 g) was slowly added drop wise over a period of 1.5 to 2
hours, to the amine solution with constant stirring. The rate of
addition of the benzoyl chloride was maintained such that the
reaction temperature was maintained less than 60.degree. C. After
complete addition of the benzoyl chloride, the reaction mixture was
gradually warmed to 85-90.degree. C. and then allowed to cool to
around 45-50.degree. C. At this point, trimesoyl chloride (16.03 g)
was gradually added to the reaction mixture such that the exotherm
did not increase the reaction temperature above 60.degree. C. After
complete addition of the trimesoyl chloride, the reaction mixture
was allowed to stir for additional 45 minutes, after which the
reaction temperature was increased to 90.degree. C. for about 30
minutes and then was cooled to room temperature. The mixture was
allowed to rest overnight at room temperature. The product was
recovered by precipitation through the addition of 1.5 L of
distilled water, which was followed by was vacuum filtration using
a filter paper and a Buchner funnel. The crude product was then
washed with acetone (250 mL) and washed again with hot water (500
mL). The product (yield: ca. 90%) was then air dried over night at
room temperature and then was dried in a vacuum oven 150.degree. C.
for 4 to 6 hours. The product was a pale tan solid. The Proton NMR
characterization was as follows: .sup.1H NMR (400 MHz
d.sub.6-DMSO): 10.68 (s, 3H, CONH), 10.3 (s, 3H, CONH), 8.74 (s,
3H, central Ar), 8.1 (d, 3H, m-phenylene Ar), 7.9 (d, 6H,
ortho-ArH), 7.51 (m, 15H, meta-para-ArH and 6H, m-phenylene Ar) and
7.36 (m, 3H, m-phenylene Ar).
Example 1
Compounds A2, B2, and C were tested for their influence on the melt
viscosity of a polymer that is commercially available from Ticona,
LLC and has the following monomer content: 63% 4-hydroxybenzoic
acid ("HBA"), 5% 2,6-hydroxynaphthoic acid ("HNA"), 16%
terephthaiic acid ("TA"), 11% 4,4'-biphenol ("BP"), and 5%
acetaminophen ("APAP"). More particularly, the polymer was heated
at 120.degree. C. and powder coated with a pentaerythritol
tetrastearate (PETS, commercial grade Lonza Glycolube P) at a 0.3
wt. % loading based on the weight of the polymer. The hot pellets
were then coated with 2 wt. % (based on polymer weight) of one of
Compounds A2, B2, or C. The mixtures were then melt mixed using a
Leistritz 18 mm co-rotating fully intermeshing twin screw extruder
having 6 temperature control zones (including at the extrusion die)
and an overall L/D of 30. A general purpose screw design was used
to compound the oligomers into a resin matrix. All materials were
fed to the feed throat in the first barrel by means of a volumetric
feeder. Materials were melted and mixed then extruded through a
single hole strand die. Material was then quenched in a water bath
to solidify and granulated in a pelletizer. The resultant pellets
were then dried for 3 hours at 120.degree. C. and scanning shear
capillary melt viscosity measurements were carried out at
350.degree. C. The results are set forth below.
TABLE-US-00002 Polymer + Polymer + Polymer + Comp. Control Compound
A2 Compound B2 Compound C Melt Viscosity 25.3 8.8 5.7 3.7 (1000
s.sup.-1) (Pa-s) Melt Viscosity 33.3 10.9 8.8 5.0 (400 s.sup.-1)
(Pa-s) Intrinsic Visc. 6.96 6.40 5.50 5.43 (dL/g) Tm (.degree. C.)
336.4 329.2 322.5 329.0 Tc (.degree. C.) 289.3 288 283.72 290.0
As indicated, a melt viscosity reduction was achieved by the
compounds of the present invention. To determine if this resulted
in a change in the mechanical properties, the pellets were also
injection molded to obtain specimen samples for tensile, impact,
flexural and heat distortion temperature measurements. The results
are set forth below.
TABLE-US-00003 Polymer + Polymer + Compound Compound Polymer +
Comp. Control A2 B2 Compound C Flexural Modulus 12,500 11,000
11,300 -- (MPa) Flexural Break 167 151 143 -- Stress (MPa) Flexural
Break 3.4 3.3 2.7 -- Strain (%) Tensile Modulus 13,150 10,550
11,800 13,400 (MPa) Tensile Break 152 146 147 146 Stress (MPa)
Tensile Break 1.74 2.18 1.86 1.65 Strain (%) Charpy Notched 90.9
75.7 65.3 65.6 (kJ/m)
As indicated, only a small change in the mechanical properties was
observed for the compositions. Without intending to be limited by
theory, it is believed that a significant reduction in mechanical
properties did not occur because the compounds did not react
directly with the polymer backbone to reduce its molecular
weight.
Example 2
A first sample (Sample 1) was formed. A 2 L flask was charged with
4-hydroxybenzoic acid (415.7 g), 2,6-hydroxynaphthoic acid (32 g),
terephthalic acid (151.2 g), 4,4'-biphenol (122.9 g), acetaminophen
(37.8 g), and 50 mg of potassium acetate. The flask was equipped
with C-shaped stirrer, a thermal couple, a gas inlet, and
distillation head. The flask was placed under a low nitrogen purge
and acetic anhydride (99.7% assay, 497.6 g) was added. The
milky-white slurry was agitated at 75 rpm and heated to 140.degree.
C. over the course of 95 minutes using a fluidized sand bath. After
this time, the mixture was then gradually heated to 360.degree. C.
steadily over 300 minutes. Reflux was seen once the reaction
exceeded 140.degree. C. and the overhead temperature increased to
approximately 115.degree. C. as acetic acid byproduct was removed
from the system. During the heating, the mixture grew yellow and
slightly more viscous and the vapor temperature gradually dropped
to 90.degree. C. Once the mixture had reached 360.degree. C., the
nitrogen flow was stopped. The flask was evacuated below 20 psi and
the agitation slowed to 30 rpm over the course of 45 minutes. As
the time under vacuum progressed, the mixture grew viscous. After
72 minutes, the final viscosity target was reached as gauged by the
strain on the agitator motor (torque value of 30 units). The
reaction was then stopped by releasing the vacuum and stopping the
heat flow to the reactor. The flask was cooled and then polymer
(Sample 1) was recovered as a solid, dense yellow-brown plug.
Sample for analytical testing was obtained by mechanical size
reduction.
A second sample (Sample 2) was formed as described for Sample 1,
except that 18.7 grams of Compound C was also introduced into the
reactor. It was observed that there were fewer residues in the
distillate as compared to Sample 1. The reaction was stopped after
72 minutes--a torque value of 50 units was observed on the agitator
motor.
The thermal properties of the melt polymerized polymers Sample 1
and Sample 2 were tested as described above. The results are set
forth below in the following table.
TABLE-US-00004 MV at MV at Tm Tc 1000 s.sup.-1 400 s.sup.-1 Sample
Additive (.degree. C.) (.degree. C.) IV (dL/g) (Pa * s) (Pa * s) 1
-- 361.6 301.8 8.4 75.7 118.2 2 C 343.0 284.7 5.0 137.8 230.1
These and other modifications and variations of the present
invention may be practiced by those of ordinary skill in the art,
without departing from the spirit and scope of the present
invention. In addition, it should be understood that aspects of the
various embodiments may be interchanged both in whole or in part.
Furthermore, those of ordinary skill in the art will appreciate
that the foregoing description is by way of example only, and is
not intended to limit the invention so further described in such
appended claims.
* * * * *